Zeolite-containing catalyst, synthesis and use thereof

ABSTRACT

A method of preparing a composition comprising a crystalline zeolite and a porous matrix material which comprises coating at least a portion of the surface of at least one of the components selected from the group consisting of said zeolite and said porous matrix material with a solid or liquid coating material which is substantially retained during any subsequent processing steps prior to its positive intentional removal, which occurs after the compositing step, intimately compositing said zeolite with said matrix material and removing said coating material; the composition prepared therefrom and hydrocarbon conversion employing the composition as a catalyst.

United States Patent Plank et al.

[451 July 11, 1972 [54] ZEOLITE-CONTAINING CATALYST,

SYNTHESIS AND USE THEREOF [72] Inventors: Charles J. Plank, Woodbury;Edward J.

[ 21 1 AppL No.: 885,288

[52] US. Cl .208/1l1, 208/120, 252/455 Z [5 1] Int. Cl. ..C10g 13/02,BOlj 11/40 [58] Field of Search ..252/455 Z; 208/1 1 l, 120, 46 MS;55/75 [56] References Cited UNITED STATES PATENTS 3,234,028 2/1966Dunham, Jr. et al .252/455 X 3,266,973 8/1966 Crowley.....

3,267,022 8/1966 Hansford ..208/lll Hansford ..208/l ll Smith ..208/ l20 Primary Examiner-C. F. Dees Atmrney-Oswald G. Hayes, Andrew L.Gaboriault, Raymond W. Barclay and James F. Woods ABSlRACT A method ofpreparing a composition comprising a crystalline zeolite and a porousmatrix material which comprises coating at least a portion of thesurface of at least one of the components selected from the groupconsisting of said zeolite and said porous matrix material with a solidor liquid coating material which is substantially retained during anysubsequent processing steps prior to its positive intentional removal,which occurs afier the compositing step, intimately compositing saidzeolite with said matrix material and removing said coating material;the composition prepared therefrom and hydrocarbon conversion employmgthe composition as a catalyst.

44 Claims, No Drawings ZEOLITE-CONTAINING CATALYST, SYNTHESIS AND USETHEREOF CROSS-REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of copending ap- 5 BACKGROUND OF THE INVENTION 1.Field of the Invention This invention relates to a process forintimately combining a crystalline zeolite material with a porousmatrix. More particularly, this invention relates to a method ofintimately combining a catalytically active zeolite material with aporous inorganic oxide matrix material to prepare an improvedcomposition having greater attrition resistance and catalystselectivity.

2. Discussion of the Prior Art Zeolite materials have heretofore beenintimately combined with porous matrix materials especially porousinorganic oxide matrixes. The purpose of combining the zeolite, which isthereafter converted to a catalytically active form, with the porousinorganic oxide matrix is to provide a hydrocarbon conversion catalystuseful especially in catalytic cracking which has greatly improvedproperties being, for example, far more active and selective than priorcatalysts. Methods for preparing such combined zeolite-porous .inorganicoxide matrix material are disclosed and claimed, for example, In U.S.Pat. No. 3,271,418 of Sept. 6, 1966, ofC. J. Plank and E. J. Rosinskientitled Catalytic Conver-sion of Hydrocarbons with a CrystallineAlumino-Silicate in a Silica-Alumina Matrix.

It has been found, however, that the catalyst properties can be improvedand enhanced by an improved method in which the zeolite is intimatelycombined or composited with the porous matrix. The results provided bythe new method include the production of a more catalytically activezeolite. Although not wishing to be bound by any theory, it is believedthat when a zeolitic molecular sieve is combined with a porous inorganicoxide matrix, that there is produced more than one type of interaction.One type of interaction occurs when compositing is accomplished in anaqueous medium and is undesirable. This interaction is not observed,however, when the present process is performed, allowing production of acatalyst having improved catalytic activity including enhanced attritionresistance and steam stability.

SUMMARY OF THE INVENTION Broadly, this invention contemplates a methodof preparing a composition comprising a crystalline zeolite and a porousmatrix material which comprises coating at least a portion of theexternal surface of said zeolite or said porous matrix material with asolid or liquid coating material which is substantially retained duringany subsequent processing steps prior to positive removal, intimatelycompositing said zeolite with said matrix material and removing saidcoating material.

DISCUSSION OF PREFERRED EMBODIMENTS The purposes of this invention canbe accomplished by coating at least the external surfaces of the zeoliteor matrix particles with any material which is sufficiently adherent tosaid surfaces that it is substantially retained during subsequentprocessing steps carried out prior to its intentional removal whichoccurs after the step of compositing said zeolite with said matrix. Thequantity of coating material added should be generally greater thanabout 1 percent by weight based on the weight of the zeolite particles.Generally, we prefer to add less than about percent by weight based onthe weight of the zeolite.

It has been found that a preferred manner of introducing a coatingmaterial into the zeolite treated in accordance with the presentinvention is to contact the zeolite with a fluid medium, e.g., asolution or suspension, preferably an aqueous solution or suspension,containing a substance which can be converted to coke or to othercarbonaceous material. For example, one can contact and coat the zeolitebeing treated with a carbonaceous material in colloidal form (e.g.,starch) maintained in suspension in a liquid medium such as water. Aftercontact, the material is treated to yield coke or other carbonaceousmaterial which forms an effective coating on the zeolite and preventsany adverse sieve-matrix interaction. Particularly good results havebeen found by this in situ coating procedure employing various sugarsand starches. In this instance, an aqueous solution of a sugar iscontacted with the zeolite being treated. The aqueous solutionintroduces the dissolved sugar into the zeolite pores and places thesame on its surface. The zeolite so treated is then heated in asubstantially non-oxidizing atmosphere at a temperature between thedecomposition point of the sugar and the decomposition point of thezeolite, preferably between 300 and about 1,200 F. This causes the sugarto be decomposed into coke or similar carbonaceous material. Thecarbonaceous material is intimately associated with the zeolite,protects the same and facilitates zeolite dispersion within the matrixwhen the same is composited with the amorphous matrix material employed.When starch is employed, the operation is substantially the same withthe exception that the starch is applied as an aqueous suspension.Nevertheless, the starch is an effective coating agent and when heatedin a substantially non-oxidizing atmosphere between its decompositionpoint and the decomposition point of the zeolite, it yields carbonaceousmaterial which functions to provide excellent dispersion of the zeolitein the porous amorphous matrix without any adverse effects. Hydrocarbonconversion runs, notably cracking, show that composite catalystsprepared with a saccharide, e.g., monosaccharide, disaccharide, orpolysaccharide are superior in terms of activity and selectivity andcompare favorably with other coating procedures contemplated herein.

Monosaccharides contemplated for use in the present invention includeglucose, fructose, mannose, galactose, aldohexose, aldopentose,glyceraldehyde, allose, altrose, talose, gulose, idose, arabinose,ribose, eylose, lyxose, erythrose, threose, hexose and rhamnose.Disaccharides which are useful in the present invention include sucrose,lactose, maltose and cellobiose. Polysaccharides which can be employedinclude cellulose, hemicelluloses, chitin and, especially, starch. Otherpolysaccharides not specifically mentioned herein can be used providedthey can be treated while present on the zeolite to yield a carbonaceouscoating agent under conditions wherein the treatment does not adverselyaffect the zeolite.

The zeolite particles to be coated should preferably have particlediameters averaging below about 10 u, preferably below about 5 u.

The technique of the present invention is especially useful in preparinghydrocarbon cracking catalysts of the fluid size, i.e., compositezeolite-matrix catalysts of a size such that they are suitable for usein fluidized bed processes wherein the catalyst particles themselvesmove through the catalytic cracking unit. This is particularly true forcomposite catalysts prepared employing sugar or starch as an in situsource of carbonaceous coating material. I-Iigher yields and improvedselectivities have been found when starches or sugars are employed inthe coating operation.

In another preferred embodiment, this invention contemplates a method ofpreparing a catalyst comprising a crystalline zeolite and a porousmatrix material which process comprises filling at least 10 percent ofthe available pore volume of a catalytically active zeolite with ahydrophobic material, compositing said zeolite with a porous inorganicoxide matrix material and removing said hydrophobic material.Preferably, at least 50 percent and still more preferably at least 75percent of the pore volume available to the hydrophobic material isfilled with said hydrophobic material. As nearly as possible, most ofthe individual particles should be at least surface coated.

The method of the present invention is similarly applicable to thepreparation of compositions comprising a porous amorphous material suchas a porous amorphous inorganic oxide catalyst which is to be dispersedin a matrix. These porous amorphous inorganic oxides catalysts includecatalysts containing silica, alumina, zirconia, beryllia, titania,magnesia, thoria and the like as well as combinations of any of thesesuch as silica-alumina, silica-magnesia, silica-thoria. Ternarycompositions such as silica-alumina-thoria, silica-alumina-zirconia,silica-alumina-magnesia and silica-magnesia-zirconia I are alsocontemplated. These compositions can be disposed in any of the matrixmaterials disclosed hereinafter. In certain instances, the catalyticcomposition will be dispersed in a matrix composition having the same orsimilar chemical properties. Nevertheless, the dispersing method of thepresent invention provides better dispersion of the catalytic materialin the matrix and improves the compositions overall attritionresistance.

Zeolites which can be coated in accordance with this invention includeboth natural and synthetic zeolites. These zeolites include gmelinite,chabazite, dachiardite, clinoptilolite, faujasite, heulandite, analcite,levynite, erionite, sodalite, cancrinite, nepheline, lazurite,scolecite, natrolite, offretite, mesolite, mordenite, brewsterite,ferrierite, and the like. Suitable synthetic zeolites which can betreated in accordance with this invention include zeolites X Y, A, L,ZK-4, B, E, F, H, J, M, Q, T, W, Z, alpha and beta. The term zeolites"as used herein contemplates not only aluminosilicates but substances inwhich the aluminum is replaced by gallium and substances in which thesilicon is replaced by germanium. Generally, these have a port sizegreater than 3 angstroms. Those most preferred are the ones having portsizes greater than 4A so that coating materials may penetrate said poreopenings.

Porous matrix materials which can be composited with any of theforegoing zeolites, as well as other zeolites not specifically mentionedabove, include porous carbon black; porous metals especially porousaluminum, clays, such as kaolinites, montmorillonites, both natural andchemically or thermally treated, gels, and porous inorganic oxidesincluding porous alumina gels and gels rich in alumina and siliceoushydrogels especially those containing another metal oxide. Suchsiliceous hydrogels include, for example, silica-alumina,silicamagnesia, silica-zirconia, silica-thoria, silica-beryllia,silicatitania, as well as ternary combinations such assilica-aluminathoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia. Particular preference is accorded cogelsof silica-alumina, silica-zirconia and silica-alumina-zirconia. In theforegoing gels, silica is generally present as the major component andthe other oxides of metals are present in minor proportion. Thus, thesilica content of the siliceous gel matrix utilized in the catalystdescribed herein will generally be within the approximate range of 55 to100 weight percent with the metal oxide content ranging from zero to 45weight percent. Siliceous hydrogels utilized herein and hydrogelsobtained therefrom can be prepared by any method well known in the art,such as, for example, hydrolysis of ethyl orthosilicate, acidificationof an alkali metal silicate wherein either the acid solution or thealkali metal silicate solution can contain a compound of a metal, theoxide of which it is desired to cogel with silica. The relativeproportions of finely divided crystalline aluminosilicate and siliceousgel matrix can vary widely with the zeolite content ranging from about Ito about 90 percent by'weight and more usually, from about 2 to 80percent and, particularly where the composite is prepared in the fomi ofbeads, in the range of about 2 to about 50 percent by weight of thecomposite.

Materials useful as coating materials for either the porous matrixmaterial or the zeolite include both solids and liquids. Among thesolids may be mentioned polymers, such as polystyrene, sulfur, wax andother high molecular weight compounds melting above about 40 C. andcoke. Of these solids, wax and coke are preferred, especially thelatter, because it can be readily removed subsequent to the compositingopera- 4 tion and is available at low cost. They can be removed from thecomposite simply by burning or other similar suitable thermal treatment.Liquids which can be used are generally those which adhere to thesurface to be coated and are not substantially removed during thesubsequent compositing and/or ion exchange steps. For example, a heavygas oil, especially a waxy gas oil, can be used for this purpose.Likewise, an organic polymer or polymerizable material can be used. Thecoating material, whether solid or liquid, must be such that it issubstantially retained during any subsequent wet-processing step, priorto its intentional removal, such as during the compositing or ionexchange steps, as it is important that during these steps the zeoliteand the matrix remain out of direct contact with one another to avoidthe aforementioned type of sieve-matrix interaction. A liquid coatingmaterial can, of course, be one which is converted to a solid coatingmaterial as, for example, by coking, freezing, polymerization and thelike. Generally, the compositing and ion exchange steps are employedusing an aqueous medium and, in that event, the coating material ishydrophobic. However, if the compositing and/or ion exchange steps areperformed in a different solvent medium, then the coating materialchosen must be such that it does not substantially dissolve in thatsolvent and thus be removed from either the sieve or the matrix.

The zeolite can be composited with the porous matrix material while in acatalytically active form such as a form wherein a major portion of thealkali metal cations have been replaced by ion exchange with a metal ormixture of metals of Groups IB VIII of the Periodic Table. Suitably, thezeolite can be in the rare earth exchange form. Additionally, ifdesired, it can be in a hydrogen form, ammonium form, alkylammoniumform, arylammonium form, or a form resulting from thermal treatment ofone of these forms at a temperature of about 700 F. for a period of atleast one minute, generally at least 10 minutes, up to a temperature ofabout l,400 F. Particularly preferred zeolites are those in which thealkali cations have been largely replaced in part by a metal, especiallyarare earth metal, and in part with hydrogen or a hydrogen precursor.

The compositing operation can be performed in any suitable mannerespecially those means disclosed in the US. Pat. No. 3,140,249. Thezeolite can be milled with the porous matrix material or can be formedby introducing coated zeolite into a hydrous oxide sol or hydrogel(e.g., a siliceous sol or alumina-containing sol or hydrogel) during theprocess of forming said sol or hydrogel. Said sol would then be formedinto a hydrogel which is thereafter calcined to provide the porousmatrix structure. If desired, the hydrogel can be formed, together withthe coated zeolite into spheroidal particles by any feasible process,such as methods described in patents to Marisic, for example, US. Pat.No. 2,384,946. Broa'dly, such methods involve introducing globules ofhydrosol into a column of water-immiscible liquid; for exam 1 ple, anoil medium wherein the globules of hydrosol set to a hydrogel andsubsequently pass into an underlying layer of water from which they aresluiced to further processing operations such as base-exchange,water-washing, drying and calcining. Larger size spheres are ordinarilywithin the range of from about one sixty-fourth to about one-fourth inchin diameter, whereas smaller size spheres, which are generally referredto as micro-spheres, are with-in the range of from about 10 to about I00microns in diameter. The latter can also be prepared by spray dryingsols or slurries. The use of the spherically shaped particles is ofparticular advantage in hydrocarbon conversion processes, including themoving catalyst bed processes and the fluidized processes in which thespheroidal gel particles are subjected to continuous movement. Asapplied to the stationary bed, spheroidal catalyst particles provideeffective contact between the reactants and the catalyst by avoidingchanneling. It is accordingly a preferred embodiment of the presentinvention to prepare the described catalyst in the form of spheres,although it is to be realized that the method of the invention can alsobe employed in obtaining a mass of catalyst which can, thereafter, bebroken up into particles of desired. size. Likewise, the methoddescribed herein can be used for the preparation of the presentcatalysts in the form of particles of any other desired size of shape.

While, for the production of spheroidal catalyst particles by theaforementioned technique, initial formation of a hydrosol which setsupon lapse of a short interval of time to an all embracing bead-formhydrogel is desirable, it is within the purview of this invention toalso employ, particularly where the catalyst is prepared in a form otherthan the spheroidal shape, a matrix comprising a gelatinous hydrousoxide precipitate with varying degrees of hydration or a mixture of ahydrogel and such gelatinous precipitate. The term gel, as utilizedherein, is intended to include hydrogel, gelatinous precipitates andmixtures of the two. Zeolite addition may occur before, during or aftergel formation.

As indicated hereinabove, the crystalline alkali metal zeolite can beion exchanged either before or after intimate admixture with the porousmatrix material. If performed subsequent to the compositing step, theion exchange technique will depend upon the condition of the zeolite andthe extent to which the pores are filled. Base exchange is affected bytreatment with a solution of a pH sufficiently high that it does notdestroy the crystallinity of the zeolite. This varies depending on thesilica/alumina ratio of the zeolite. The solution will, of course,contain an ion capable of replacing an alkali metal cation. Theexchangeable alkali metal content of the final catalytic compositeshould be less than about 1 and preferably less than about 0.5 percentby weight. The exchangeable alkali metal content of the final catalystis determined by the test set forth in U.S. Pat. No. 3,271,418. The baseexchange solution can be contacted with the zeolite in the form of afine powder, a compressed pellet, extruded pellet, spheroidal bead orother particle shape. Base exchange required for introducing thenecessary re-placing ions is carried out on the combined zeolite matrixcom-posite for a sufficient period of time and under appropriatetem-perature conditions to replace at least 75 percent of theexchangea-ble alkali metal originallycontained in the zeolite and toeffectively reduce the exchangeable alkali metal content of theresult-ing composite to below about 1 weight percent. It is contemplatedthat any ionizable compound of a metal capable of replacing the alkalimetal can be employed for base exchange either alone or in combinationof other ions. These metals are generally metals of Groups 1B VIII ofthe Periodic Table, especially metals of Groups 11 and Vlll of thePeriodic Table and manganese. The composition can have at least aportion of its alkali metal content converted to a hydrogen form bytreating the same with inorganic or organic acids. Additionally, thefinished composite material can be converted into an ammonium formutilizing an aqueous solution of an ammonium salt in which the ammoniumcation ionizes and replaces alkali metal ions in the composite. Suchsolutions include ammonium hydroxide and ammonium sulfate. The ammoniumform is converted to the hydrogen form by heating the same at atemperature of at least about 500 F. causing evolution of ammonia andretention of a proton in the composition.

The crystalline zeolite porous matrix composite especially in a metal,other than alkali metal, hydrogen, ammonium, alkyl-ammonium orarylammonium form can be activated by thermal treatment. This treatmentis generally performedby heating one of these forms at a temperature ofat least 700 F. for at least 1 minute and generally need not be longerthan 20 hours. While superatmospheric pressure can be employed duringthe thermal treatment, atmospheric pressure is generally used forreasons of convenience. It is frequently preferred to perform thethermal treatment in the presence of moisture, although the presence ofmoisture is not necessary. The thermal treatment can be performed at atemperature up to about l,750 F. care being taken to stay below thedecom The method in which the coating material is removed after eitherthe compositing or ion exchange step depends upon the nature of thecoating material employed. As indicated above, when coke is used to coatthe sieve or matrix material and fill at least 10 percent of the pores,it can be removed, simply, by burning the resultant composite. When ahydrophobic liquid such as a heavy gas oil is employed as a coatingmaterial, it is suitably removed by burning or by use of a solvent ofthe same. Additionally, depending upon the nature of the coatingmaterial, it can be removed by cracking, thermal treatment orsublimation. This also applies when materials such as paraffins andpolymers are employed as coating materials.

While one of the primary advantages of the present process resides ineliminating adverse zeolite-inorganic oxide matrix interaction, asecondary effect of the coating procedure is to permit the crystallinezeolite to be more finely subdivided, as by milling, and/or maintainedin a finer state of subdivision in that coating prevents the zeoliteparticles from reagglomerating during the compositing step. Thisprovides a composite catalyst which, when a coating material is removed,has the zeolite particles more finely dispersed and distributed withinthe porous matrix and leads to greatly improved attrition resistance.Thus, the process of this invention is useful in dispersing crystallinezeolites even in porous matrixes which are not characterized by anyparticular matrix-sieve interac tion. In this category, there are porousmetals, such as porous aluminum, and porous carbon black.

In order to more fully illustrate the nature of this invention and themanner of practicing the same, the following examples are presented.

Except where otherwise noted, the catalytic properties of the subsequentexamples were determined by cracking a Mid- Continent Wide Range gas oil(whose properties are given in Table l) in a static bed unit at about900 F. at atmospheric pressure, a space velocity (LHSV) 4 and acatalyst/oil ratio of 1.5 for a 10 minute period.

TABLE 1 Properties of Mid-Continent Gas Oil Charge Stock Wide Range GasOil Vol.% on crude 44-89 Gravity, APl 29.6 Aniline No., F. 181 S, wt.%0.52 N, wt.% 0.046 Pour point, F. Carbon residue, wt.% 0.19 Ni, p.p.m.0.17 Cu, p.p.m. 0.46 V, p.p.m. 0.26 H wt.% 12.77

Distillation, F. ASTM V.A.

lBP 497 458 5%, vol. 552 551 10% 570 577 20% 593 601 30% 615 630 40% 640665 50% 668 705 60% 695 752 70% 713 798 80% 732 854 740 919 947 EP 750Vacuum assay corrected to 760 mm.

EXAMPLE I A. A rare earth exchanged Linde zeolite Y (REY)-c1ay (kaoline)composite was prepared by ball milling the REY with the clay for 4 hhours. Its preparation specifics are given in subparagraph B below. Thecomposite contained 10 percent by weight REY having a sodium content of0.9 percent by weight. It was then dried, pelleted and crushed to 4 X 10Tyler mesh particles.

B. A second composite containing silica was prepared by first ballmilling another portion of the same rare earth exchanged zeolite Y with10 percent by weight silica as hydrogel for 3 16 hours and the combiningthe resultant composite with kaolin clay and ball milling again. Therare earth exchanged zeolite Y component in this preparation was madefrom a sodium form of Linde zeolite Y byexchanging with RECl -6BY2O to alow residual sodium content. This was .per-

formed in a laboratory by exchanging semi-continuously with a 10 percentRECl -6I-l O at about 180 F. to about 23 percent sodium and then dryingat 270 F. The dried material was then re-exchanged with RECl -6H O to aresidual sodium content of 0.90 weight percent sodium. In addition, thisrare earth exchanged zeolite Y contained 17.2 weight percent (RE) O 18.9weight percent A1 and 61.7 weight percent SiO This rare earth exchangedzeolite Y (REY) was calcined for 10 hours at 1,000 F. prior to use inthe composite. In preparing the composite catalyst, 60 grams of theabove REY was blended with 571 grams of silica hydrogel having 10.5weight percent SiO ('determined at 1,000 F.) and 1342 cc. H O in a highshear blendor followed by a 3 :5 hour ball milling in a 1.1 gallon millcontaining 8 pounds of stones. To. this slurry was then added 552 gramsMcNamee clay (a kaolin clay 87 percent solid determined at 1,000" F.)and milled an additional hour. This slurry was then air dried at 230 F.overnight for about 20 hours, pelleted and sized to 4 X 10 Tyler meshand calcined for 10 hours at 1,000 F. followed by steaming at l,200 F.with steam at psig. for 72 hours. Physical properties and evaluationdata are summarized in Table 2 below.

C. In a manner similar to the procedure set forth in subparagraph B, aREY-silica/alumina-clay composite catalyst was prepared. The amount ofsilica/alumina was 10 percent by weight based on the weight of the finalcomposite.

D. In the manner of subparagraph B, a REY-alumina-clay composite wasprepared.

All four catalysts were tested for physical properties after treatingwith 100 percent steam for 72 hours at 1,200 F. and 15 psig. as well asafter treating with 5 percent steam for 24 hours at 1,575 F. andatmospheric pressure. Catalytic cracking results are given in the tablebelow.

TABLE 2 REY-Clay (Kaolinite)Hydrogel Interaction (10% Rey) Steamed 72hours/l200F/15 psig. Catalyst A B C D Hydrogel (10%) None SiO SiO,/ A1 0A1 0 Surface area (m /g) 62 65 69 63 Crystallinity REY) 9.6 11.0 8.3Conversion (Vol. 63.4 61.1 59.1 62.9 C, Gasoline (Vol.%) 55.6 53.7 50.054.6 Steamed 24 hours/5% steam] 1575Fll atm Surface area (mlg) 48 54 5251 Crystallinity REY) 4.5 4.1 4.1 4.6 Conversion (Vol.%) 59.6 49.6 49.453.5 C Gasoline (Vol.%) 50.4 43.6 42.5 46.6

' being cracked using a composite catalyst and to improve theselectivity of the cracking to C gasoline, several different compositecatalysts were prepared employing the coating procedure of thisinvention. First, direct comparison was made with the catalysts of Table2 employing the same rare earth exchanged Linde zeolite Y; but, in thiscase, the REY had a substantial portion of its pore volume filled withcoke. The amount of coke on the aluminosilicate was about 15-18 percentby weight. Deposition of the coke on zeolite was achieved by saturatingthe aluminosilicate with a gas oil then heating it in a flask under anitrogen blanket at 700 F. for 2-3 hours. The coated zeolite was thenball milled in water slurry with the indicated hydrogel-clay. The claythat was employed was a kaolinite clay known as McNamee Clay.

In Table 3, set forth below, the cracking results of catalysts preparedby pro-coking the zeolite and the catalyst prepared without pro-cokingthe zeolite are set forth. The hydrocarbon charge was Mid-Continentalgas oil and the catalysts were steamed for 72 hours at 1,200 F. and 15psig.

TABLE 3 Effects of Pre-coking on REY-Hydrogel Interaction (Steamed 72hours/1200F./l5 psig.)

The important result noted from the table above is the very substantialgain in catalytic activity caused by the pre-coking operation. Theamount of activity gained is approximately equivalent to an increase of50 percent in sieve effectiveness. This estimate is based on the changeof conversion obtained when the amount of REY zeolite used in aconventional sievematrix composite catalyst was increased from 7.5percent to 13.3 percent by weight. This increase in conversion was from59.6 percent to 66.4 percent. Thus, at the 60 percent conversion level,an increase of about 1 percent in conversion results from a 1 percenthigher sieve content.

EXAMPLE 2 In the manner of Example 1 D, a rare earth-exchanged zeoliteX-alumina-kaolinite composite catalyst was similarly prepared withoutpre-coking. In Table 4 below, it is compared with a catalyst preparedwith the pre-coking step. The catalysts were steamed for 72 hours atl,200 F. and 15 psig.

TABLE 4 Effect of Pre-coking on REX-A1 0 Interaction (Steamed 72hours/l,200 F/15 psig) Pre-coked No Yes Surface Area (mlg) 55 53Conversion (Vol. 42.3 50.0 C Gasoline (Vol.%) 37.0 42.9

From the above results, it can be seen that a marked improvement isobtained both in conversion and in selectivity when the catalyst isprepared by pre-coking the zeolite prior to the compositing step.

The effects of presaturating the zeolite crystals to be used in thecomposite catalysts comprising silica-alumina gel were determined inseveral different series of tests.

EXAMPLE 3 1n the first group, all were prepared as bead-type catalystsfrom the same batch of rare earth exchanged zeolite Y (REY). Allcontained 7.6 percent REY calcined for 10 hours at 1,000 F. and 40percent a A1 fines (about 4 microns) which had been calcined at atemperature of about 1,200 C. and is known as A-3 alumina and theremainder (matrix) was a sil; ica-alumina gel containing 94 percent SiOand 6 percent A1 0 the gel bead being prepared at 8.5 pH.

1n this group of catalysts, three different types of preparations werecarried out. The differences are defined by the method of treating theREY. These treatments were as follows:

1. standard no treatment after the rare earth exchange drying andcalcining,

2. REY coking with wide range Mid-Continent gas oil,

3. REY heavy waxy gas oil.

The coking with the wide range Mid-Continent gas oil was performed bycontacting the zeolite crystals with an excess of the same and thenheating the material in a flask under a nitrogen blanket at 700 F. for2-3 hours. When heavy gas oil was employed as the coating material, onepart of gas oil by weight was added to one part of zeolite at 200 F. Itwas then mixed with an A-3 alumina fines slurry and charged to a ballmill. Milling was continued for 24 hours. All three of these beadpreparations were split into two batches. The first was base exchangedby continuous flow of one-half volume of solution per volume of hydrogelper hour with 1.4 weight percent solution of (NI-19 80 and the secondwith solutions containing 1 weight percent Al (SO.,) -l8 H 0 and 0.2weight percent (NH SO Each was water washed until free of solublecations, dried 20 hours at 450 F., and calcined for 10 hours at l,000 F.The following describes in detail the preparation of the above-describedcatalysts.

CATALYST 3 A The rare earth exchanged zeolite Y (REY) component of thiscatalyst was prepared by base exchanging 7.34 pounds (44.5 percentsolids at l,000 F.) sodium form of Linde Y (Na 9.97 weight percent, A1 020.7 weight percent, SiO 64.9 weight percent) with 1.21 pounds RECl -6 H0 in 25.50 pounds water for 1 hour at 200 F., water washing with 2,600ml. water and oven drying at 450 F. in air overnight (about 20 hours).This contact was repeated again giving a final residual sodium of 1.5weight percent. Prior to use in the bead catalyst preparation, the REYcomponent was calcined for 10 hours at 1,000 F.

The bead catalyst preparation employing the listed solutions was asfollows:

Silicate Solution Solution A 6.96 lbs. of Q-Brand sodium silicate (28.9weight percent SiO 8.9 weight percent Na O, 62.2 percent H 0) 100 lbs.of water Solution B 0.31 lbs. REY (1.5 percent Na) calcined for 10 hoursat 1.64 lbs. A -Al O milled for 24 hours in 21.4 percent slurry 6.02lbs. water A 5.3 g. of a dispersant compound of a salt of ligninsulfonic acid containing 11 weight percent Na O, 0.4 weight percent CaOand 0.5 weight percent MgO and having a pH between 7.0 and 7.5, todisperse the fines.

Solution B was mixed into Solution A forming a mixture having SpecificGravity 1.264 at 76 F.

Acid Solution 57.1 lbs. ofwater 4.23 lbs. ofA; Al,,),'18 11 0 1.98 lbs.of H 80, 97 percent Sp. Gr. 1.056 at 79 F.

These two solutions were mixed together through a mixing nozzle using396 cc per min. of silicate solution at 70 F. and 358 cc per min. ofacid solution at 42 F. The resulting hydrosol had a 8.5 pH and gelledinto hydrogel in 2.4 seconds at 67 F. Gelation was carried out in aconventional beadforming process to produce spheroidal hydrogelparticles.

The composition of the resulting catalyst (on a 1,000" F. calcinedbasis) at the point of forming was calculated to be:

3.0 wt. A1 0 matrix 94.2 weight percent 49.4 wt. SiO SiO 5.8 weightpercent A1 0 7.6 REY 40.0 wt. A Al O The processing of this catalystfirst involved base exchange continuously with a 1.4 weight percent(NH,,) SO solution at room temperature over a 24 hour period. Thesolution flow rate was about one-half volume per volume of catalyst perhour. Following the base exchange, the hydrogel was water washedessentially free of sulfate ion, dried 20 hours at 450 F., followed bycalcination in air for 10 hours at 100 F., and steamed for 24 and 72hours at 1,200 F. with steam at 15 psig. Physical, chemical andcatalytic properties of the catalyst are summarized in Table 5 below.

Catalyst 3B was prepared using the same bead hydrogel prepared above in3A, but base exchanging with a solution containing 1.0 weight percent Al(SO,) '18H O and 0.2 weight percent (NI-10 80 Further, processing,activation and evaluation was the same as discussed above and alsosummarized in Table 5 below.

Catalysts 3C and 3D were prepared by the same bead preparation methoddiscussed in the previous two samples, 3A and 3B differing only in thatthe same REY component was coked by slurrying with wide-rangeMid-Continent gas oil and heated at 750 F. until all volatile componentswere removed. This coked REY was dispersed in the silicate solution asdescribed above.

Catalyst 3C was base exchanged in the same manner as 3A while Catalyst3D was base exchanged in the same manner as Catalyst 38.

Catalysts 3E and 3F were prepared in a manner quite similar to thatdiscussed under 3A and 3B differing only in that the same calcined REYwas saturated with a waxy gas oil. This REY saturated with gas oil wasthen ball-milled with an aqueous slurry of A-3 alumina fines, previouslydescribed, prior to dispersion in the silicate solution.

These catalysts were tested catalytically after being steamed both 24and 72 hours with percent steam at 1,200 F. and 15 psig. The catalyticcracking results of Mid-Continent gas oil are compared in Table 5. Inaddition, some were tested for the cracking of a recycle stock whoseproperties are given in Table 6. The catalytic data are given in Table7.

Catalyst activities as measured in the cracking of wide rangeMid-Continent gas 011 (Table 5) vary substantially with the method ofpreparation. The catalysts prepared using the pre; treatingtechnique-coking or saturation with heavy gas oilshow definite advantagein initial activity and also stability to steam treatment. This is shownby comparing Catalyst 38 with Catalyst 3F in Table 5. ln addition,Catalyst 3D was substantially better in terms of conversion andselectivity than Catalyst 38 in cracking the catalytic cycle stock asshown in Table 7. After steaming for 72 hours, Catalyst 3D gives a 4.4percent increase in conversion and a 3.9 percent increase in C Gasolineat substantially the same coke yield. This represents a very substantialselectivity gain.

It should be pointed out here that coking is representative of processesinvolving coating the zeolite particles with an organic polymericmaterial. Other organic polymers or polymerizable compounds will work aswell.

230 F. and calcined for hours at 1,000 F. The product analyzed 0.9weight percent sodium, 61.7 weight percent silica, 17.2 weight percentrare earth oxide and 18.9 weight percent alumina. The composites wereallowed to equilibrate at room temperature with atmospheric water atabout 50 percent relative humidity prior to X-ray analysis.

The REX-containing reference composites were prepared in a similarmanner. The REX zeolite component was prepared from commerciallyavailable Linde Zeolite X which was thrice. exchanged'with an aqueousrare earth solution at 160 F. The weight ratio of total rare earthchloride to NaX was about 1. The final product, after washing, had about1.2 weight percent exchangeable sodium. The weight percent RE O was 26.After exchange, it was dried at 250 F. and steamed at 1,100 F. for 45minutes in a flow of steam at one atmosphere. The moisture content ofthe resultant product was 2.1 weight percent.

1n the case of both types of composites, X-ray analysis was performed byscanning from 7 twice angle theta to 5 twice l 1 12 The various percentscrystallinity expressed above, express the percent crystalline zeolitecomponent present in the comlBP 516 401 posite catalyst. Thesecrystallinities are determined from comi3 2%; 2?; parisons of X-raydiffraction patterns of the above prepara- 612 630 tions with X-raydiffraction patterns of composites having 5 23 37 known zeolite content.528 643 TABLE 5.CRAGKING MID-CONTINENT GAS OIL Catalyst 3A 3B 3C 3D 3E3F Steaming hours 24 72 24 72 24 72 24 72 24 72 24 72 Composition:

Na, weight percent 0.08 0.08 0.08 0.09 0.08 0 09 (RE); OWe1gh1;t'lereenl'tfl 1.55 1.38 1.66 1.42 1.47 1 38 Physical properties:

App. Dens.g./cc.i 0.72 0.80 0.73 0.77 0. 77 0.83 Surface area, m./g.steamed" 116 96 100 75 116 96 111 96 113 102 80 X-ray analysis:

crystallinity calcined. 9.5 13.1 9.1 8.3 7.9 7.1 crystallinity percentste 5.9 6.1 9.1 7.9 7.5 7.5 Conversion, Volume percent. 49. 8 48 5 56. 151. 6 58. 9 57. 7 61. 1 59. 3 55. 7 57. 0 56.9 56.9 C5 plusgasoline,volume pereen 42.9 40 2 48.9 45.7 51.1 49.8 52.4 51.5 48.8 48.8 49.949.6 Total C4s, volume percent. 10.0 9.3 10.9 9.0 11.5 11.1 12.7 11.010.5 11. 1 10.8 10.6 Dry gas, weight percent 4.4 5.4 5.1 5.4 5.0 5.1 5.65.4 4.7 5.1 4.8 5.4 Coke, weight percent 1.5 1.3 1.1 1. 2 1. 2 1.3 1.31.4 1.3 1.4 1.4 1.3 LSA (attrition resistance) seconds required for 50percent weight fines 270 413 255 465 765 1, 310

1 With steam at 15 p.s.i.g. and at 1,200 F. V w 7 V REY-containingreference composites were prepared by 50% 634 648 blending known amountsof REY with the same type of 28,? gig amorphous material. The REY usedin these reference com- 80% 656 672 posites was prepared from a sodium Yprepared according to 90% 668 691 U.S. Pat. No. 3,130,007 which waswater washed at 180 F. to 700 703 pH 11, base exchungedwith 10 weightpercent RECl.,-6H O 30 Percent 9 (VOL) I Percent Rcslduc (Vol) 1.3aqueous solution for six l-hour contacts. The exchanged pcrcem [ms (VOL)()1 product was filtered, water washed at 180 F. until chloride free,dried at 250 F. in air, base exchanged using 10 weight percent RECl -6HO aqueous solution for four l-hour con- 35 TABLE7 tacts. The product wasfiltered, washed chloride free, dried at Cracking Cycle Stock Conditions4Ll-lSV, 1.5 Cat/oil, about 900F., 10 min./run

Catalyst 38 3D Steaming Hoursl 72 72 Conversion, Vol.% 30.2 34.6C,+Gaso1ine, Vol.% 23.6 27.5 Total C s, Vol.% 5.7 6.0 Dry Gas, wt.% 3.33.6 Coke, Wt.% 1.3 1.4

Steaming 72 hours at 1200 F. with steam at 15 psig.

A summary of crystallinity data taken from Table 5 is presented below:

c 1 llinit angle theta. The peak height at 6. 1 was measured inmillimeryb a ysteamed ters. The percent crystallinity is the CatalystCalcined 24 Hours eak hei ht of sam lo p g p X 100 percent. peak heightof standard composite Treatment Standard A 9.5% 5.9 The 6.1 line waschosen because 11'] these patterns it is the most standard 3 3 61 i tPre-Coked C 9.1% 9.1 pro en Pre-coked D 8.3% 7.9

Saturated TABLE 6 Gas Oil E 7.9% 7.5 Satu t d Composition of RefineryCycle Stock 65 Gas S F 71% 2:1 83 These data clearly indicate thatpre-saturating the REY with Aniline No. F. 141.0(mixed) 7O coke or witha heavy, waxy gas oil greatly improves cyrstallini- Ammatlcsy tyretention when the catalysts are exposed to steam. The g g f 09 wtcrystallinity was calculated by use of X-ray diffraction pat- Nitrogen(Kjeldahl) 0.047 wt.% temS- Carbon Residue (Conradson) 0.04 wt.% At thesame time the attrition resistance (Lawson Shaker Refraction lndex at20C. 1.53887 AS Vacuum Assay (10mm) Attrition or LSA) is very highcompared to the standard when the treated zeolite particles aresubsequently milled as in 3E and 3F. The standard for these two formsgave the values of 270 and 418 seconds required to generate 50 weightpercent fines whereas the catalyst prepared by coating with the heavygas oil followed by ball milling gave attrition resistance measurementsof 765 and 1310 for the two ion exchanged forms. Attrition resistancewas determined in accordance with the method set forth in US. Pat. No.3,301,794. to Cramer et al. entitled, Process for Manufacturing ImprovedCatalytic Particles," Jan. 3 l, 1967, column 8, lines 37-63. Thus, fromthese measurements of the physical properties of catalysts prepared bythe pre-coking technique of this invention, it is apparent that thecomposite catalyst is characterized by having a greater degree ofdispersion of the sieve particles throughout the catalyst matrix. Suchbenefits have particular application in utilizing the catalyst in liquidphase hydrocarbon conversion reactions, especially hydrocracking andcracking of residua.

EXAMPLE 4 Two other samples were .prepared using the composite formingprocess discussed under Example 3A above.

These preparations differ from the general process in that the REYcomponent was derived from an aluminum-deficient sodium form of zeoliteY (NaY). Alumina removal from the NaY was achieved by treating 11.42pounds of the sodium form of zeolite Y (43.8 percent solids at 1,000 E),having a composition of Na, 10.3 weight percent SiO 61.6 weight percent,Al O 21.6 weight percent, SiO /Al O 4.86, twice at 200 F. for 24 hourswith an ethylenediaminetetraacetic acid solution H EDTA, (442 g. H EDTAin 4420 g. H O). This aluminum deficient sodium zeolite Y was thencontacted three times with a RECl -6H O solution. Each of the threecontacts was for 1 hour duration at 200 F. using 1 equivalent rare earthper equivalent sodium per contact assuming a starting sodium level of 7weight percent. Actually, 916 g. RECl '6H O in 52 pounds water were usedin each contact. After each contact, the sieve was washed with 4 litersof water and dried at 270 F. overnight for about 20 hours. The finalcomposition of this H, EDTA treated and RECl -6H O exchanged NaY was0.26 percent Na, 16.6 percent A1 16.8 percent (RE) O and 62.1 percentSiO thus the SiO. ,/Al,0 molar ratio was 6.3. Prior to use in, theforming operation, the aluminum-deficient REY was calcined for 10 hoursat 1,000 F.

The bead-forming operation for this example consisted of first mixingthe following solutions:

Silicate Solution Solution A 12.2 pounds Q-Brand sodium silicate (28.9weight percent SiO 8.9 weight percent Na O 62.2 weight percent water)1.75 pounds water Solution B 0.542 pounds calcined REY (described abovein this exam- 2.8 7 pounds of A-3 A1 0 fines 10.52 pounds water 9.43 g.Marasperse N Solution B was ball-milled for 4 hours.

Solution B was added to Solution A.

Sp. Gr. 1.272 at 79 F.

Acid Alum Solution 57.10 pounds H O 4.23 pounds Al (SO.,) 1 81-1 0 1.98pounds H 80 (97 percent) Sp. Gr. 1.059 at 75 These solutions were mixedtogether through a nozzle adding the 384 ml. per minute of silicatesolution at about 70 F. to 326 ml. per minute acid alum flow at 40 F.,forming a hydrosol having a 2.3 second gel time at 67 F. and a pH of8.4. The calculated composition at this point after calcining at 1,000F. was 7.6 weight percent REY, 40.0 weight percent A- 3 alpha aluminawhich had been previously calcined at about- [200 C. in a matrix of 94.5percent SiO and 5.4 percent A1 0,.

The resulting bead hydrogel was processed continuously witha 1.4 weightpercent (NH SO., solution as discussed under Example 3A.

Physical, chemical and catalytic properties of this catalyst Sample 4Aare summarized in the table below.

The catalyst Sample 4B was prepared by a process essentially identicalto that used in Sample 4A, differing only in that the aluminum deficientREY was coked by saturation with Mid-Continent gas oil followed byheating at 750 F. until all vapors were removed.

The catalysts were steamed for 24 hours at 1,200 F. and under a steampressure of 15 psig. prior to evaluation. The results of cracking theMid-Continent gas oil are set forth in Table 8.

TABLE 8.BEAD CATALYST PREPARATION WITH ALUMI- NUM DEFICIENT CRYSTALLINEALUMINOSILICATE [Evaluated with Mid-Continent gas oil] CatalystSteaming, in hours 24 24.

gormrgng pH 8.4 8.4.

tion: s/185211)! Sl/Al 94%. SiOz-6% A1 03.

1 F Iypm Standard REY- Pre-coked REY.

Cone. ZTYDQ--- AsAlzOs AaAlzOa E Cleric Base xc ange:

Solution (NHmSOl Conc.,weight percent 1.4 Composition: Na, weightpercent 0.08 0.10. (RE) O ,Weight percent- 1.24 1.28. Physicalproperties: Surface area,

mfig 116 111. Catalytic evaluation [Mid-Continent gas oil]:

Conditions, LHSV 4 4. Conditions, CIO...i 1.5 1.5.

Conversion v0 ume percent 49.0 52.7. 05 plus gasoline, vo ume percent44.0 46.2. Total 04's, volume percent 8.1-. Dry gas, weight percent..4.2 Coke, weight percent"--. 1.1-. Hz, weight percent 0.01. Difiusivity.59 30.6.

LSA (attrition resistance) EXAMPLE 5 The following catalysts will serveto illustrate the preparation of fluid catalysts containing the cokepretreated sieve component.

Catalyst 5C was prepared by dispersing REY crystalline aluminosilicateinto a 60 percent SiO,-40 percent clay matrix. The preparation detailsconsist of first dispersing 2.08 pounds of kaolin (McNamee) clay in 46pounds water then adding 9.15 pounds N-Brand sodium silicate (28.9weight percent SiO 8.9 weight percent Na O, 62.7 weight percent H O).This dispersion is heated to F. and acidified with H 80, with 165 ml.conc. H 80. (97 weight percent The reaction mixture was held for 2 hoursat F. After this initial aging, the pH was reduced to about 4.2 withadditional H SO (requiring another 162 ml. con. H 80 This mixture wasallowed to cool to room temperature overnight while stirring.

To this silica-clay matrix slurry was then added 220 g. calcinedchelated REY (same as that used in Example 4.4). The REY was dispersedin 660 cc. water containing 66 g. RECl '6BY2O prior to addition to thesilica-clay matrix slurr This slurry containing the REY was then spraydried with inlet temperature of 650 F. and outlet temperature of 280 F.

Product composition calculated from components at this point was 10percent REY and 90 percent silica-clay matrix (60 percent SiO -40percent clay).

The final spray-dried product was base exchanged with a percent (NI- 80using about gallons of solution for about 2 quarts of fluid catalyst,washed essentially free of sulfate ion, dried at 250 F. for 24 hours.

This catalyst was evaluated both under two distinct test conditions assummarized in the Table below. To be evaluated at the first set ofconditions, it was necessary to pellet the fluid catalyst then calcineit at l,000 F. for 10 hours followed by steaming at 1,200 F. with steamat 15 psig. for 24 hours. For fluid evaluation this fluid catalyst wascalcined for 10 hours at 1,000 F. then steamed for 4 hoursat 1,400 F.with steam at atmospheric pressure.

The finished catalyst had a residual sodium of 0.06 weight percent and a(RE) O content of 1.24 weight percent. After the 15 psig. steaming at1,200 F., the surface area was 136 while after the 1,400 F., 4 hoursteam treat, the surface area was187 m /g.

Catalyst SD was prepared in essentially the same manner as thatdescribed for sample 5C differing only in that the same 1aluminum-deficient REY was first coked at 750 F. with Mid- ContinentWide-range gas oil. Catalysts 5A and 5B were prepared in the same manneras Catalysts 5C and 5D with the exception that only 5 weight percentrare earth zeolite Y was incorporated into the catalysts.

The residual sodium content of this preparation SD was 0.10 weightpercent Na and a (RE) O content of 1.86. The surface area of thepelleted catalyst steamed 24 hours at l,200 F. with 15 psig. steam was178 m /g. while the steamed fluid catalyst treated at 1,400 F. for 4hours with steam at atmos heric pressure had a surface data of 190 m /g.

TESTS OF FLUID TYPE CATALYSTS* Static Bed Test (4 (5 LHSV, 5 C/O, 2.4minutes, about 925F., 1 atmosphere) Conversion (vol%) 67.6 73.9 77.082.1 Gasoline (C (vol.%) 57.6 61.8 61.9 62.5 Total C 's(vol.%) 13.6 15.617.7 20.2 Dry Gas (Wt.%) 5.8 6.6 7.6 8.7 Coke (On Charge) (Wt.%) 2.2 2.63.4 5.1 Coke (On Catalyst) (Wt.%) 0.38 0.44 0.58 0.87

The catalysts were steamed 24 hours at 1200 F. and 15 psig. for thestatic bed runs and 4 hours at 1400 F. and atmospheric pressure for theFluid Catalytic Cracking-Test.

Once again the gain in activity obtained by the pre-coking technique issubstantial. One very interesting phenomenon to note is that in thefluidized cracking test, the pre-coked catalyst having 5 percent REYgives as much gasoline as the non-coked catalyst having 10 percent REY.At the same time its product distribution is much better, i.e., muchless dry gas and coke are formed. Probably Catalyst D would look muchbetter in the fluid test at higher space velocity conditions.

Cracking, utilizing catalysts, described herein, can be carried out atcatalytic cracking conditions employing a temperature within theapproximate range of 700 to 1,200 F. and under a pressure ranging fromsub-atmospheric pressure up to several hundred atmospheres. The contacttime of the oil within the catalyst is adjusted in any case according tothe conditions, the particular oil feed and the particular resultsdesired to give a substantial amount of cracking to lower boilingproducts. Cracking may be affected in the presence of the instantcatalyst utilizing well-known techniques including, for

example, those wherein the catalyst is employed as a fluidized mass oras a compact particle-form moving bed, as well as in a static bed, orriser cracker.

Employing a catalytically active catalyst prepared by the presentinvention containing a hydrogenation component, heavy petroleum residuastocks, cycle stocks, and other hydrocrackable charged stocks can behydrocracked at temperatures between 425 F. and 950 F. using molarratios of hydrogen and hydrocarbon charge in the range between 2 and 80.The pressure employed will vary between 10 and 2,500 psig. and theliquid hourly space velocity between 0.1 and 10.

Similarly using such a catalyst, reforming stocks can be reformedemploying a temperature between 700 F. and 1,000 F. The pressure can bebetween and 1000 psig., but is preferably between 200 and 700 psig. Theliquid hourly space velocity is generally between 0.1 and 10, preferablybetween 0.5 and 4 and the hydrogen to hydrocarbon mole ratio isgenerally between 1 and 20, preferably between 4 and 12.

From the foregoing, it is apparent that the coating technique of thepresent invention provides significant advantages in the catalystpreparation providing catalysts which are capable of greater conversionin cracking of hydrocarbon stocks and in greater selectivity in crackingcycle stocks which are difficult for conventional catalysts to crack ata high conversion rate. The catalyst prepared by the present techniqueprovides these better selectivities after being treated with steam whichtreatment simulates conditions which cracking catalysts would undergoafter a period of time in a conventional catalytic cracking unit.Additionally, the method of this invention provides improved dispersionof the sieve particles in the porous matrix and improves the attritionresistance of the catalyst so prepared. Accordingly, the present processis highly valuable for preparing catalysts to be used in refineries. Itwill also be noted that the method of this invention can be performedusing relatively inexpensive coating materials normally available at therefinery site. The process can be used to improve properties ofdessicants or adsorbents in which case it is not necessary that thealkali metal content be greatly reduced by ion exchange.

The advantages obtained when fluid and pelletted catalysts are preparedusing sugarand starch-coated zeolites are clearly shown by comparing thefollowing pairs of Examples 6 and 7, 8 and 9, and 10 and 11. Examples 6,8 and 10 use non-coated zeolites whereas 7, 9 and 11 utilize sugarandstarch-coated zeolites. The fluid catalyst matrix employed in thefollowing preparations was made to contain 60 weight percent silica and40 weight percent clay. The aqueous slurry of silica-clay mixture ispartially neutralized with H SO, then heat treated at 140 F. for 2 hoursfollowed by further acid neutralization to 4.5-4.8 pH. The activecomponent is incorporated into this slurry at this point followed byspray drying, processing by exchange with (NHQ SO and then dehydratingand steaming.

EXAMPLE 6 In preparing this catalyst 2.48 pounds of Georgia kaolin clay,86.5 weight percent solids, was dispersed in 52.2 pounds water. To thisclay dispersion was added 10.98 pounds N- Brand sodium silicate, 28.9weight percent SiO, 8.9 weight percent Na O, while stirring vigorously.This mixture was then heated to F. at which point 198 cc of concentratedH SO (97.6 percent) was added over a half hour period. After thisinitial partial neutralization, the mixture was heated at F. for 2hours. After this heat treatment, the mixture was further neutralizedwith concentrated H 50. to a pH of 4.5-4.8 requiring an additional cc ofacid.

To the above matrix slurry was added a ballmilled rare earth Ycrystalline aluminosilicate which is equal to 10 weight percent activecomponent on final catalyst basis. The rare earth Y crystallinealuminosilicate was prepared by exchanging a com mercially availablesodium Y aluminosilicate semi-continuously at about l60-180 F. with rareearth chloride hexahydrate to a residual sodium content of 3.19 weightpercent. This active component was further calcined continuously in arotary calciner at about l,200 F. prior to wet milling 4 hours with anequal weight of kaolin clay. In the ballmilling step, 350 g. of thecalcined REY was wet milled for 4 hours with 350 g. Georgia kaolin clayin 2,800 cc water with some dispersant. A sufficient amount of thismilled slurry was dispersed in the above silica-clay matrix mixture togive 10 weight percent active REY in the final catalyst. The finalmixture of matrix and active component was subsequently dried in a spraydryer with an air inlet temperature of about 550 F. and an outlettemperature of 300 F.

Processing of the spray dried product involved 2 slurry contacts withexcess water followed by settling and decantation. After this initialwater wash the product was contacted continuously with a weight percent(NH SO solution, charging 15 gals. over a 12" bed, in a 4-5 hour periodand then water washing continuously until essentially free of sulfateions. An additional exchange with RECl -6l-l O (59 g. RECLt 6H O in5.000 cc water. 1']; hour contact at room temperature) was used toreplenish exchanged rare earth.

The final catalyst had a residual sodium content of 0.12 weight percentand an (RE),O content of 2.1 weight percent.

EXAMPLE 7 This example was prepared by the method described in detailunder Example 6 differing in that the active calcined rare earthcrystalline aluminosilicate was wet milled with added sugar and RECl 6HO. The wet milling details involve milling 350 g. of calcined REY (3.19percent Na), 350 g. Georgia kaolin clay, 117 g. RECl -6H O, 88 g. sugarin 2,800 cc water for 4 hours. Enough of this milled slurry, 3,040 g.,was used to give weight percent active component in the final catalyst.

Matrix preparation, crystalline aluminosilicate dispersion, catalystprocessing and activation were essentially similar to that described inExample 6.

The final catalyst had a residual sodium content of 0.06 percent and an(RE O content of 2.2 percent.

Prior to evaluation, the catalysts were first calcined at 1,000 F. thensteamed. One sample, in each case, was steamed at l,400 F. for 4 hoursat atmospheric pressure and another for 5 hours at psig.

Comparative catalytic data summarized in Table 9 show the catalyticadvantages for catalyst Example 7, which was prepared with sugarcoatedcrystalline aluminosilicate, in both activity and selectivity. It gavehigher conversion at the same condition for the same crystallinealuminosilicate content, and produced a higher level of gasoline (CJ),63.5 vs. 59.9, at about the same coke make on charge, 2.4 weight percentcompared to 2.2.

Furthermore, it should be apparent that the catalyst containingsugarcoated REY was also more stable to severe steam treat (5 hours at1,400 F. with 15 psig steam) still showing a high activity after thesteam treat.

In the following pair of examples the advantage of other carbohydrates,such as starch, as coating materials is clearly shown.

EXAMPLE 8 In preparing the catalyst of this example, the method outlinedin Example 6 was followed incorporating an active component (rare earthY crystalline aluminosilicate having 3.1 weight percent Na) that wascalcined in the laboratory at 1,300 F. for one-half hour into asilica-clay matrix.

The final catalyst had a residual sodium content of 0.05 and an (RE) Ocontent of 2.0 weight percent.

This final catalyst was steamed and evaluated as described under Example6. Catalytic evaluation data are summarized in Table 10.

EXAMPLE 9 The silica-clay matrix used in this catalyst was prepared asdescribed under Example 6. The active component employed in preparingthis example was the same starting rare earth Y crystallinealuminosilicate used in Example 8. This active component as wet cake1,120 g. (44.5 percent solids at 1,000 F.) was mixed with 50 g. starchdissolved in 700 cc. water, and

.then heated at 900 F. for 10 hours to insure complete coking of thestarch coating. Enough of this active component was dispersed in waterwith added dispersant and mixed into the silica-clay matrix as describedin Example 6. This mixture was spray dried, washed, exchanged with(Nl-L,) SO, and RECl 6H O, dried, calcined and steamed as describedunder Example 6.

The final catalyst had a residual sodium content of 0.04 and an (RE) Ocontent of 2.66 weight percent.

Catalytic evaluation data comparing Example 8 (containing uncoatedactive component) and Example 9 (containing the starch coated activecomponent) are summarized in Table 10. These catalytic data again showthe advantages for surface coating the active component prior todispersing in a matrix. Catalyst (Example 9) of exceptional activity andselectivity can be prepared as is apparent from data in Table 10.

The following catalysts were prepared in extruded form employing thesame active components used in preparing Examples 6 and 7. Enough wasadded to produce a composite containing 10 weight percent REY. Thisactive component was mixed with clay and extruded into three-sixteenthsinch pellets.

EXAMPLE 10 ln preparing this example, 79.2 g. (63.2 percent solids atl,000 F.) of the same active component, wet milled rare earth Ycrystalline aluminosilicate clay mixture, used in preparing Example 6,was blended with 231 grams of Georgia kaolin clay (86.4 weight percentsolids), cc water in a muller mixer. This wet mixture was extrudedhydraulically through a die having 3/16" holes, requiring 7-10 tonpressure on the 4 inch diameter piston. The extrudate was cut into 14;inch length, dried at 230 F., calcined for 10 hours at l,000 F. followedby steaming at 1,200 E. and 15 psig for 24 hours.

The final steamed catalyst had a surface area of 56 m /g.

The steamed catalyst was evaluated for catalytic cracking of a Wide CutMid-Continent gas oil at 4 LHSV, 1.5 C/O, 875 F. with a 10 minute run.Catalytic results are summarized in Table 11.

EXAMPLE 1 1 This example was prepared as described under Example 10differing in that the active component was the same sugarcoated materialused in fluid catalyst Example 7. In preparing this catalyst, 79.2 g. ofthe active component (63.2 weight percent solids), 231 g. Georgia kaolinclay (86.4 weight percent solids at l,000 F.) and 85 cc Water were mixedin a muller mixer, extruded, sized, dried, calcined and steamed asdescribed in Example 10.

The final steamed catalyst, having a surface area of 58 m /g, wasevaluated as described in Example 10.

Catalytic data presented in Table 11 clearly show the catalyticadvantages resulting from the sugar surface coating. Catalyst (Example11) has a much higher activity 70.3 volume percent as compared to 58.5.In addition, the higher yield is obtained at only a slight increase incoke pointing out the advantages in selectivity.

Catalyst of Examples 6 7 Description:

Matrix Silica-clay 60/40 (Fines Type 3 REY 3 REY Conc 10 Type Clay (Geora kaolin) Conc 10 gi 0 1 0 Composition:

Na, weight percent 0. 12 0. 06 (RE)203, Weight percent 2. 10 2. 2Physical properties steamed:

SF4 172 185 PSF5 138 143 l 5 4 hr. steam treat at 1,400 F. Steam at 0p.s.i.g.

Catalytic evaluation stock- Wide out mid-continent gas oil Conditions: 1

3 Temperature, F 4 922 4 024 Conversion, volume percent 7. 15 74. 0 Cl-gasoline, weight percent. 50. 9 63. 5 Total Cis, volume percent. 15.215. 7 Dry gas, weight percent..- 5. 8 6. 1 Coke, weight pereent 2.2 2. 4He, weight percent 0. 02 0. 01

5 hrstream treat at 1,400 F.

Steam at 15 p.s.i.g.

M Wide cut mid-continent gas oil Catalytic evaluation stock Conditions:

WHSV 8.34 8. 34 o o 3 3 Temperature, F 4 927 4 924 Conversion, volumepercent 67. 6 71. 5 C5+gasoline, volume percent 59. 7 63. 0 Total C-|s,volume percent 12. 7 12. 7 Dry gas, weight percent 4. 9 5. 4 Coke,weight percent 1. 7 1. 8 lb, weight percent. 0. 01 0. 002 35 REY andclay milled together for 4 hours in aqueous slurry along with minoramount of dispersant for 4 hours.

2 REY and clay milled with REClILfiHZO and sugar in aqueous slurry for 4hours.

1 3.19 wt. percent Na.

4 2.4 min. run.

Nora:

SF4-steamed for 4 hours at 1,400 F. and 0 p.s.i.g. PSF5-steamed for 5hours at 1,400 F. and 15 p.s.i.g. WHSV--weight hourly space velocitTABLE 10 Example 8 9 Description:

atrix Silica-clay 60/40 Fines (1):

Type 1 REY 2 REY Cone 10 10 Fines (2) Type Cone Composition:

Na, wt. percent 0.05 0.04 (RE) O wt. percent 2.0 2.66 Physicalproperties surface area,

mJ/g. steamed:

SF 210 PSF5 157 171 Steam treat 4 hrs. at 1,400 F.

with 0 p.s.i.g. steam Catalytic evaluation stock Wide out mid-continentgas oil Conditions:

WIISV- 8. 3 8.34 3 3. 0 024 924 73.5 70.7 0 gasoline, vol. pereen 64. 666. 0 Total Cis, vol. percent 12. 5 16. 3 Dry gas, wt. percent 5.5 6. 5Coke, wt. percent 2.6 2.9 H Wt. percent 0.01 0.02

Steam treat 5 hrs. at 1,400 F.

with 15 p.s.i.g. steam Catalytic evaluation stock Wide cut mid-continentgas oil Conditions:

WHSV 8. 3 8. 3 C/O 3.0 3.0 Temp, F 927 024 Conv., vol. percent 70.1 75.6 C gasoline, vol. percent 62. 0 64. 8 Total Cis, vol. percent 12.1 14.3 Dry gas, wt. percent. 4. 9 6. l Coke, wt. percent. 2. 0 2. 2 Hg, wt.percent 0.01 0.01

Table l0(ominued TABLE 11.COMPARISON OF EXTRUDED CATALYST CON- TAININGUNCOATED AND STARCH COKE COATED REY Catalyst of Examples 10 11 Steaming:

Description:

Matrix Georgia kaolin clay Fines:

(1) Type 1 REY 1 REY Cone 10 10 Physical properties surface area,

infi/g. steamed 56 58 Catalytic evaluation. Wide cnt mid-continent gasoil Conditions:

LlISV 4 4 C/O 1. 5 l. 5 Temp, 1 875 875 Conversion, vol. puree 58. 5 70..i Ct gasolimnvol. percent... 48. 4 50. 7 Total Cis, vol. percent 14.013. 5 Dry gas, wt. percent 4. 7 ll. 0 Coke, wt. percent 2. 3 2. 0 H2,wt. percent 0. 01 0. 01

The terms and expressions used herein are used for purposes ofdescription and not of limitation, as there is no intention, in the useof such terms al.

8. A method according to claim 7 wherein said zeolite contains less thanabout 1 weight percent exchangeable alkali metal and has a pore sizegreater than about 4 angstroms.

9. A method according to claim 7 wherein the surfaces of the zeolitecomponent are coated apart from the matrix.

10. A method according to claim 7 wherein the surface of one of saidcomponents is coated in the presence of the other of said components.

11. A method according to claim 7 wherein the quantity of 7 gas oilcorresponds to that which would fill at least 10 percent of the porevolume of a catalytically active zeolite.

12. A method according to claim 7 wherein the quantity of gas oilcorresponds to that which would fill at least 50 percent of the porevolume of a catalytically active zeolite.

13. A process according to claim 4 wherein said zeolite is chosen fromthe group consisting of Zeolite X and Zcolite Y.

14. A process according to claim 8 wherein said zeolite is chosen fromthe group consisting of X and Y.

15. A process according to claim 13 wherein said zeolite has at leastsome of its cations exchanged into a rare earth form.

16. A process according to claim 4 wherein said zeolite is in itshydrogen form.

17. A process according to claim 6 wherein said porous matrix is aninorganic oxide material chosen from the group consisting of porousinorganic oxides, mixtures and compounds thcreof.

18. A process according to claim 15 wherein said inorganic oxide ispredominantly silica.

19. A process according to claim 17 wherein said inorganic oxide ispredominantly alumina.

20. A process according to claim 17 wherein said inorganic oxidematerial is a silica-alumina gel.

21. A process according to claim 17 wherein the inorganic oxidecomponent is a clay material chosen from the group consisting of rawclays, chemically treated clays and thermally treated clays.

22. A method according to claim 1 wherein the coating is formed bycontacting the surface of the zeolite with a saccharide and treating theso coated zeolite to form a carbonaceous coating on the zeolite.

23. A method according to claim 21 wherein the zeolitc is contacted withan aqueous sugar solution and the so treated zeolite is heated at atemperature between the decomposition point of the sugar and thedecomposition point of the zeolite.

24. A method according to claim 22 wherein the zeolite is contacted withan aqueous suspension of a starch and the so treated zeolite isthereafter heated at a temperature between the decomposition point ofthe starch and the decomposition point of the zeolite.

25. A method according to claim 23 wherein the temperature is between300 and l,200 F.

26. A method according to claim 24 wherein the temperature is between300 and 1,200 F.

27. A method according to claim 22 wherein the sacchan'de is amonosaccharide.

28. A method according to claim 22 wherein the saccharide is apolysaccharide.

29. A method according to claim 22 wherein the saccharide is adisaccharide.

30. A composition prepared by the method of claim 1.

31. A composition prepared by the method of claim 3.

32. A composition prepared by the method of claim 4.

33. A composition prepared by the method of claim 7.

34. A composition prepared by the method of claim 13.

35. A composition prepared by the method of claim 22.

36. A method for converting a hydrocarbon charge which comprisescontacting said hydrocarbon charge under hydrocarbon conversionconditions with a catalyst comprising the composition of claim 30.

37. A method for cracking a hydrocarbon charge which comprisescontacting said hydrocarbon charge under cracking conversion conditionswith a catalyst comprising the composi-' tion of claim 32.

38. A method for cracking a hydrocarbon charge which comprisescontacting said hydrocarbon charge under cracking conversion conditionswith a catalyst comprising the composition of claim 33.

39. A method for cracking a hydrocarbon charge which comprisescontacting said hydrocarbon charge under cracking conversion conditionswith a catalyst comprising the composition of claim 35.

40. A method for hydrocracking a hydrocarbon charge which comprisescontacting said hydrocarbon charge under hydrocracking conditions with acatalyst comprising the composition of claim 35.

41. A method for cracking which comprises contacting said hydrocarboncharge under cracking conditions which include a temperature within therange or 700 to 1,200 F. and a pressure ranging from subatmosphericpressure up to several hundred atmospheres with a catalyst comprisingthecomposition of claim 30.

42. A method of hydrocracking which comprises contacting saidhydrocarbon charge under hydrocracking conditions including atemperature between 425 F. and 950 F., a hydrogen to hydrocarbon moleratio in the range between 2 and 80, a pressure between 10 and 2,500psig. and a liquid hourly space velocity between 0.1 and 10 with acatalyst comprising the composition of claim 30.

43. A method of preparing a composition comprising a catalyticallyactive porous amorphous material and a porous matrix material whichcomprises coating at least a portion of the external surface of saidporous amorphous material with a coating material selected from thegroup consisting of polystyrene, wax, carbonaceous material derived froma saccharide, sulfur, coke and gas oil which is substantially retainedduring any subsequent wet processing steps prior to being intentionallyremoved, intimately compositing said porous amorphous material with saidmatrix material and removing said coating material.

44. A method according to claim 43 wherein said porous amorphousmaterial comprises an inorganic oxide.

- @FMCE 1 ETA Th3? ctRTu-rtirt or QCBEQ'HCN Patent No. [3,676,330 IDated July 11, 1972 I Inventofls) Charles J., Plank and. Edward J.Rosinski It is cartifiod that error appears in tho above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 7, line 8 "the" combining should be --then-- combining Column 7,line 13 "RECl.6BY20" should be --REC .65 e-- Column 7, line 49 "(10%Reshould be --(lO%REY)-- Column 10, line A "A; 1 11 9 should .be -A1 (soColumn 10, line 15-16 "3.0 wt A1203 matrix 94.,2 weight L9JL wt% S10percent SiO 5.,8

weight percent A1 0 should read --3.0- wt A1 0 matrix 9&2 weigl".

49,4 wt% S10 percent S10 5c weight percent Column 11, 1st para. Firstparagraph should begin after Table 5 in Column 11, not before Table 5,column 313, 72 "5.4" should be MA-- Table 5, last line Column 313,second No. L13" should be "418-- Column 11, 12, Table 6 Table 6 split upinto sections,

should be together o-mso Pm No. 3, 7 ,330

Inventofls) Charles J. Plank and Edward J. Rosinski It is certified thaterror apprs in the above-identified patent and that said Letters Patentare hereby corrected as shown below:

Table 8, last line "256" should be "254" Column 14, line 73 "REc1.6BY20" should be --RECl ,6H O- Column 14, line 73 "slurr" should be--slurry--- Column 15, line 31L "data" should be --area Column 15, line#8 after "007" insert --0.9 0.9 1.2-- Column 19, line 35 "0.002" shouldbe --0.02--

Column 19, line 43 '"velocit" should be --velocity-- Column 20, line 31after "terms" delete "a1. and insert -and expressions, of excluding anyequivalent or portions thereof, as many modifications and departures arepossible within the scope of the invention claimed.--'-

Column 20, line 32 insert the word --'-CLAIMS-- and insert the followingclaims:

1. A method of preparing a composition comprising a crystalline zeoliteand a porous matrix material which comprises coating at least a portionof the surface of said zeolite or said porous matrix material with acoating material selected from the group consisting of polystyrene, wax,carbonaceous material derived from a saccharide, sulfur, coke and gasoil which is substantially retained during any subsequent wet-processingPo-wso new: No. 3,676,330 Dated July 11, 1972 Inventor g Charles Ja and.Edward. Jo ROSinSki It is cattifiad that error appears in theshow-identified patant and that: said Letters azent are hereby correctedas shown below:

steps prior to positive removal, which occurs after the compositingsteps, intimately compositing said zeolite with said matrix material andremoving said coating material,

2. A method of preparing a catalytic composition according to Claim 1comprising a zeolite contained in and distributed throughout a porousmatrix which comprises coating a. substantial portion of the surfaces ofat least one of the components selected from the group consisting ofsaid zeolite and the material comprising said matrix apart from theother component with a substance capable of preventing intimate contactbetween the surfaces of said zeolite and porous matrix material uponintermixture of the same, thereafter combining said zeolite and matrixmaterial and subsequently removing said substance from the resultingcomposite.

3. A method according to Claim 2 wherein the component which is coatedis a crystalline zeolite,

L. A method of preparing a catalytic composition according to Claim 3wherein said zeolite contains less than about 1 weight percentexchangeable alkali metal and a pore size greater than 1 Angstroms.

5, A method according to Claim 3 wherein the quantity of coatingmaterial added is at least 1 percent by weight based on the weight ofthe zeolite component.

Ymtmlt No. 33 7 733 Datad July 97 Inventofls) Charles J. Plank andEdward J9 Rosinski 4 It is cartifiad that error spprs in thaabove-identified patent and that amid Letters Patent are herebycorrectad am shown below:

6. A method according to Claim 3 in which the quantity of coatingmaterial added corresponds to the amount which would fill at least 10percent of the pore volume of the zeolite component.

7., A method of preparing a. composition comprising a crystallinezeolite and a porous matrix material which comprises coating at least aportion of the surface of said zeolite or said porous matrix materialwith an adherent gas oil which is substantially retained during anysubsequent wet-processing steps prior to its positive removal,intimately compositing said zeolite with said matrix material andremoving said coating materialo Column 20, claim 8 "LL angstroms" shouldbe "LL Angstroms- Column 20, claim 17 claim 6" should be --Claim 5--Column 20, claim 18 claim 15" should be-Claim l7-- Column 20, claim 23"claim 21" should be "claim 22-- Column 22, claim 41 "range or" shouldbe --range of-' line 3 Signed and sealed this 9th day of January 1973.

(SEAL) ttest:

EDWARD M.FLETCHER,JR= Attesting Officer @GTTSCHAIK cr-msiloner ofPatents

2. A method of preparing a catalytic composition according to claim 1comprising a zeolite contained in and distributed throughout a porousmatrix which comprises coating a substantial portion of the surfaces ofat least one of the components selected from the group consisting ofsaid zeolite and the material comprising said matrix apart from theother component with a substance capable of preventing intimate contactbetween the surfaces of said zeolite and porous matrix material uponintermixture of the same, thereafter combining said zeolite and matrixmaterial and subsequently removing said substance from the resultingcomposite.
 3. A method according to claim 2 wherein the component whichis coated is a crystalline zeolite.
 4. A method of preparing a catalyticcomposition according to claim 3 wherein said zeolite contains less thanabout 1 weight percent exchangeable alkali metal and a pore size greaterthan 4 angstroms.
 5. A method according to claim 3 wherein the quantityof coating material added is at least 1 percent by weight based on theweight of the zeolite component.
 6. A method according to claim 3 inwhich the quantity of coating material added corresponds to the amountwhich wouLd fill at least 10 percent of the pore volume of the zeolitecomponent.
 7. A method of preparing a composition comprising acrystalline zeolite and a porous matrix material which comprises coatingat least a portion of the surface of said zeolite or said porous matrixmaterial with a gas oil which is substantially retained during anysubsequent wet-processing steps prior to its positive removal,intimately compositing said zeolite with said matrix material andremoving said coating material.
 8. A method according to claim 7 whereinsaid zeolite contains less than about 1 weight percent exchangeablealkali metal and has a pore size greater than about 4 angstroms.
 9. Amethod according to claim 7 wherein the surfaces of the zeolitecomponent are coated apart from the matrix.
 10. A method according toclaim 7 wherein the surface of one of said components is coated in thepresence of the other of said components.
 11. A method according toclaim 7 wherein the quantity of gas oil corresponds to that which wouldfill at least 10 percent of the pore volume of a catalytically activezeolite.
 12. A method according to claim 7 wherein the quantity of gasoil corresponds to that which would fill at least 50 percent of the porevolume of a catalytically active zeolite.
 13. A process according toclaim 4 wherein said zeolite is chosen from the group consisting ofZeolite X and Zeolite Y.
 14. A process according to claim 8 wherein saidzeolite is chosen from the group consisting of X and Y.
 15. A processaccording to claim 13 wherein said zeolite has at least some of itscations exchanged into a rare earth form.
 16. A process according toclaim 4 wherein said zeolite is in its hydrogen form.
 17. A processaccording to claim 6 wherein said porous matrix is an inorganic oxidematerial chosen from the group consisting of porous inorganic oxides,mixtures and compounds thereof.
 18. A process according to claim 15wherein said inorganic oxide is predominantly silica.
 19. A processaccording to claim 17 wherein said inorganic oxide is predominantlyalumina.
 20. A process according to claim 17 wherein said inorganicoxide material is a silica-alumina gel.
 21. A process according to claim17 wherein the inorganic oxide component is a clay material chosen fromthe group consisting of raw clays, chemically treated clays andthermally treated clays.
 22. A method according to claim 1 wherein thecoating is formed by contacting the surface of the zeolite with asaccharide and treating the so coated zeolite to form a carbonaceouscoating on the zeolite.
 23. A method according to claim 22 wherein thezeolite is contacted with an aqueous sugar solution and the so treatedzeolite is heated at a temperature between the decomposition point ofthe sugar and the decomposition point of the zeolite.
 24. A methodaccording to claim 22 wherein the zeolite is contacted with an aqueoussuspension of a starch and the so treated zeolite is thereafter heatedat a temperature between the decomposition point of the starch and thedecomposition point of the zeolite.
 25. A method according to claim 23wherein the temperature is between 300* and 1,200* F.
 26. A methodaccording to claim 24 wherein the temperature is between 300* and 1,200*F.
 27. A method according to claim 22 wherein the saccharide is amonosaccharide.
 28. A method according to claim 22 wherein thesaccharide is a polysaccharide.
 29. A method according to claim 22wherein the saccharide is a disaccharide.
 30. A composition prepared bythe method of claim
 1. 31. A composition prepared by the method of claim3.
 32. A composition prepared by the method of claim
 4. 33. Acomposition prepared by the method of claim
 7. 34. A compositionprepared by the method of claim
 13. 35. A composition prepared by themethod of claim
 22. 36. A method for converting a hydrocarbon chargewhich comprises conTacting said hydrocarbon charge under hydrocarbonconversion conditions with a catalyst comprising the composition ofclaim
 30. 37. A method for cracking a hydrocarbon charge which comprisescontacting said hydrocarbon charge under cracking conversion conditionswith a catalyst comprising the composition of claim
 32. 38. A method forcracking a hydrocarbon charge which comprises contacting saidhydrocarbon charge under cracking conversion conditions with a catalystcomprising the composition of claim
 33. 39. A method for cracking ahydrocarbon charge which comprises contacting said hydrocarbon chargeunder cracking conversion conditions with a catalyst comprising thecomposition of claim
 35. 40. A method for hydrocracking a hydrocarboncharge which comprises contacting said hydrocarbon charge underhydrocracking conditions with a catalyst comprising the composition ofclaim
 35. 41. A method for cracking which comprises contacting saidhydrocarbon charge under cracking conditions which include a temperaturewithin the range or 700* to 1,200* F. and a pressure ranging fromsubatmospheric pressure up to several hundred atmospheres with acatalyst comprising the composition of claim
 30. 42. A method ofhydrocracking which comprises contacting said hydrocarbon charge underhydrocracking conditions including a temperature between 425* F. and950* F., a hydrogen to hydrocarbon mole ratio in the range between 2 and80, a pressure between 10 and 2,500 psig. and a liquid hourly spacevelocity between 0.1 and 10 with a catalyst comprising the compositionof claim
 30. 43. A method of preparing a composition comprising acatalytically active porous amorphous material and a porous matrixmaterial which comprises coating at least a portion of the externalsurface of said porous amorphous material with a coating materialselected from the group consisting of polystyrene, wax, carbonaceousmaterial derived from a saccharide, sulfur, coke and gas oil which issubstantially retained during any subsequent wet processing steps priorto being intentionally removed, intimately compositing said porousamorphous material with said matrix material and removing said coatingmaterial.
 44. A method according to claim 43 wherein said porousamorphous material comprises an inorganic oxide.